Bismuth

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This article is about the chemical element. For other uses, see Bismuth (disambiguation).

Bismuth, 83Bi
Bismuth
Pronunciation/ˈbɪzməθ/ ​(BIZ-məth)
Appearancelustrous brownish silver
Standard atomic weight Ar°(Bi)
Bismuth in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Sb
↑
Bi
↓
Mc
lead ← bismuth → polonium
kJ/mol
Heat of vaporization179 kJ/mol
Molar heat capacity25.52 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 941 1041 1165 1325 1538 1835
Atomic properties
Arabic alchemists (before AD 1000)
Isotopes of bismuth
Main isotopes[6] Decay
abun­dance half-life (t1/2) mode pro­duct
207Bi synth 31.55 y
β+
207Pb
208Bi synth 3.68×105 y β+
208Pb
209Bi 100% 2.01×1019 y α
205Tl
210Bi trace 5.012 d
β−
 		210Po
α
206Tl
210mBi synth 3.04×106 y α
206Tl
 Category: Bismuth
| references

Bismuth is a

thermally conductive
metals known.

Bismuth was long considered the element with the highest atomic mass whose nuclei do not spontaneously decay. However, in 2003 it was discovered to be extremely weakly

primordial isotope, bismuth-209, undergoes alpha decay with a half-life about a billion times the estimated age of the universe.[7][8]

Bismuth metal has been known since ancient times. Before modern analytical methods bismuth's metallurgical similarities to lead and tin often led it to be confused with those metals. The etymology of "bismuth" is uncertain. The name may come from mid-sixteenth century Neo-Latin translations of the German words weiße Masse or Wismuth, meaning 'white mass', which were rendered as bisemutum or bisemutium.

Bismuth compounds account for about half the global production of bismuth. They are used in cosmetics; pigments; and a few pharmaceuticals, notably bismuth subsalicylate, used to treat diarrhea.[8] Bismuth's unusual propensity to expand as it solidifies is responsible for some of its uses, as in the casting of printing type.[8] Bismuth, when in its elemental form, has unusually low toxicity for a heavy metal.[8] As the toxicity of lead and the cost of its environmental remediation became more apparent during the 20th century, suitable bismuth alloys have gained popularity as replacements for lead. Presently, around a third of global bismuth production is dedicated to needs formerly met by lead.

History and etymology

Bismuth metal has been known since ancient times and it was one of the first 10 metals to have been discovered. The name bismuth dates to around 1665 and is of uncertain etymology. The name possibly comes from obsolete German Bismuth, Wismut, Wissmuth (early 16th century), perhaps related to Old High German hwiz ("white").[9] The Neo-Latin bisemutium (coined by Georgius Agricola, who Latinized many German mining and technical words) is from the German Wismuth, itself perhaps from weiße Masse, meaning "white mass".[10][11]

The element was confused in early times with tin and lead because of its resemblance to those elements. Because bismuth has been known since ancient times, no one person is credited with its discovery. Agricola (1546) states that bismuth is a distinct metal in a family of metals including tin and lead. This was based on observation of the metals and their physical properties.[12]

Miners in the age of alchemy also gave bismuth the name tectum argenti, or "silver being made" in the sense of silver still in the process of being formed within the Earth.[13][14][15]

Bismuth was also known to the

Incas and used (along with the usual copper and tin) in a special bronze alloy for knives.[16]

Alchemical symbol used by Torbern Bergman (1775)

Beginning with

Torbern Olof Bergman, the distinctness of lead and bismuth became clear, and Claude François Geoffroy demonstrated in 1753 that this metal is distinct from lead and tin.[14][18][19]

Characteristics

Left: A bismuth hopper crystal exhibiting the stairstep crystal structure and iridescent colors, which are produced by interference of light within the oxide film on its surface. Right: a 1 cm3 cube of unoxidised bismuth metal

Physical characteristics

Pressure-temperature phase diagram of bismuth. TC refers to the superconducting transition temperature

Bismuth is a brittle metal with a dark, silver-pink hue, often with an

its oxide forms yellow fumes.[18] Its toxicity is much lower than that of its neighbors in the periodic table, such as lead and antimony.[20]

No other metal is verified to be more naturally

thermal conductivity (after manganese, neptunium and plutonium) and the highest Hall coefficient.[22] It has a high electrical resistivity.[18] When deposited in sufficiently thin layers on a substrate, bismuth is a semiconductor, despite being a post-transition metal.[23] Elemental bismuth is denser in the liquid phase than the solid, a characteristic it shares with germanium, silicon, gallium, and water.[24] Bismuth expands 3.32% on solidification; therefore, it was long a component of low-melting typesetting alloys, where it compensated for the contraction of the other alloying components[18][25][26][27] to form almost isostatic bismuth-lead eutectic
alloys.

Though virtually unseen in nature, high-purity bismuth can form distinctive, colorful hopper crystals. It is relatively nontoxic and has a low melting point just above 271 °C, so crystals may be grown using a household stove, although the resulting crystals will tend to be of lower quality than lab-grown crystals.[28]

At ambient conditions, bismuth shares the same layered structure as the metallic forms of

body-centered cubic Bi-V at 7.7 GPa. The corresponding transitions can be monitored via changes in electrical conductivity; they are rather reproducible and abrupt and are therefore used for calibration of high-pressure equipment.[31][32]

Chemical characteristics

Bismuth is stable to both dry and moist air at ordinary temperatures. When red-hot, it reacts with water to make bismuth(III) oxide.[33]

2 Bi + 3 H2O → Bi2O3 + 3 H2

It reacts with

oxyhalides with the formula BiOX.[37]

4 Bi + 6 X2 → 4 BiX3 (X = F, Cl, Br, I)
4 BiX3 + 2 O2 → 4 BiOX + 4 X2

Bismuth dissolves in concentrated sulfuric acid to make bismuth(III) sulfate and sulfur dioxide.[33]

6 H2SO4 + 2 Bi → 6 H2O + Bi2(SO4)3 + 3 SO2

It reacts with nitric acid to make bismuth(III) nitrate (which decomposes into nitrogen dioxide when heated[38]).[39]

Bi + 6 HNO3 → 3 H2O + 3 NO2 + Bi(NO3)3

It also dissolves in hydrochloric acid, but only with oxygen present.[33]

4 Bi + 3 O2 + 12 HCl → 4 BiCl3 + 6 H2O

Isotopes

Main article: Isotopes of bismuth

The only primordial

billion times longer than the current estimated age of the universe.[8] Owing to its extraordinarily long half-life, for all presently known medical and industrial applications, bismuth can be treated as if it is stable and nonradioactive. The radioactivity is of academic interest because bismuth is one of a few elements whose radioactivity was suspected and theoretically predicted before being detected in the laboratory.[8] Bismuth has the longest known alpha decay half-life, although tellurium-128 has a double beta decay half-life of over 2.2×1024 years.[42] Bismuth's extremely long half-life means that less than approximately one-billionth of the bismuth present at the formation of the planet Earth would have decayed into thallium
since then.

Six isotopes of bismuth with short half-lives (210 through 215 inclusive) occur within the natural radioactive disintegration chains of actinium, radium, thorium, and neptunium, and more have been synthesized experimentally. (Although all primordial 237Np has long since decayed, it is continually regenerated by (n,2n) knockout reactions on natural 238U.)[43][44]

Commercially, the radioactive isotope bismuth-213 can be produced by bombarding radium with bremsstrahlung photons from a linear particle accelerator. In 1997, an antibody conjugate with bismuth-213, which has a 45-minute half-life and decays with the emission of an alpha particle, was used to treat patients with leukemia. This isotope has also been tried in cancer treatment, for example, in the targeted alpha therapy (TAT) program.[45][46]

Chemical compounds

Main article: Bismuth compounds
Bismuth(III) oxide powder

Chemically, bismuth resembles arsenic and antimony, but is much less toxic.[20] In almost all known compounds, bismuth has oxidation state +3; a few have states +5 or −3.

The

complex anions,[50][51] and NaBiO3 is a strong oxidising agent.[51] The trisulfide is common in bismuth ore.[48]

Similarly, bismuth forms all possible trihalides, but the only pentahalide is BiF5. All are

Lewis acids.[33] Bismuth forms several formally-BiI halides; these are complex salts with unusually-structured polyatomic cations and anions.[50][52]

Bismuth oxychloride (BiOCl) structure (mineral bismoclite). Bismuth atoms are shown as grey, oxygen red, chlorine green.

In strongly acidic

Bismuth nitrate (not oxynitrate) is famous as one of the few aqueous-insoluble nitrate
salts.

Bismuth forms very few stable

Dirac insulator.[58][59]

Occurrence and production

See also: List of countries by bismuth production
Bismite mineral
Chunk of a broken bismuth ingot

In the Earth's crust, bismuth is about twice as abundant as gold. The most important ores of bismuth are bismuthinite and bismite.[18] Native bismuth is known from Australia, Bolivia, and China.[60][61]

World bismuth production, 2022, in tonnes
Country Refining[62]
China 16,000
Laos 2,000
South Korea 950
Japan 480
Kazakhstan 220
Other 350
Total 20,000

According to the United States Geological Survey (USGS), 10,200 tonnes of bismuth were produced worldwide by mining and 17,100 tonnes by refining in 2016. Since then, USGS does not provide mining data for bismuth, considering them unreliable. Globally, bismuth is mostly produced by refining, as a byproduct of extraction of other metals such as lead, copper, tin, molybdenum and tungsten, though the refining-to-mining ratio depends on the country.[63][64][65][66]

Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the

Betts process. Bismuth will behave similarly with another of its major metals, copper.[64] The raw bismuth metal from both processes contains still considerable amounts of other metals, foremost lead. By reacting the molten mixture with chlorine gas the metals are converted to their chlorides while bismuth remains unchanged. Impurities can also be removed by various other methods for example with fluxes and treatments yielding high-purity bismuth metal (over 99% Bi).[67]

Price

World mine production and annual averages of bismuth price (New York, not adjusted for inflation).[68]

The price for pure bismuth metal has been relatively stable through most of the 20th century, except for a spike in the 1970s. Bismuth has always been produced mainly as a byproduct of lead refining, and thus the price usually reflected the cost of recovery and the balance between production and demand.[68]

Prior to World War II, demand for bismuth was small and mainly pharmaceutical — bismuth compounds were used to treat such conditions as digestive disorders,

sexually transmitted diseases and burns. Minor amounts of bismuth metal were consumed in fusible alloys for fire sprinkler systems and fuse wire. During World War II bismuth was considered a strategic material, used for solders, fusible alloys, medications and atomic research. To stabilize the market, the producers set the price at $1.25 per pound ($2.75 /kg) during the war and at $2.25 per pound ($4.96 /kg) from 1950 until 1964.[68]

In the early 1970s, the price rose rapidly as a result of increasing demand for bismuth as a metallurgical additive to aluminium, iron and steel. This was followed by a decline owing to increased world production, stabilized consumption, and the recessions of 1980 and 1981–1982. In 1984, the price began to climb as consumption increased worldwide, especially in the United States and Japan. In the early 1990s, research began on the evaluation of bismuth as a nontoxic replacement for lead in ceramic glazes, fishing sinkers, food-processing equipment, free-machining brasses for plumbing applications, lubricating greases, and shot for waterfowl hunting.[69] Growth in these areas remained slow during the middle 1990s, in spite of the backing of lead replacement by the United States federal government, but intensified around 2005. This resulted in a rapid and continuing increase in price.[68]

Recycling

Most bismuth is produced as a byproduct of other metal-extraction processes including the smelting of lead, and also of tungsten and copper. Its sustainability is dependent on increased recycling, which is problematic.[70]

It was once believed that bismuth could be practically recycled from the soldered joints in electronic equipment. Recent efficiencies in solder application in electronics mean there is substantially less solder deposited, and thus less to recycle. While recovering the silver from silver-bearing solder may remain economic, recovering bismuth is substantially less so.[71]

Dispersed bismuth is used in certain stomach medicines (

pearlescent cosmetics (bismuth oxychloride), and bismuth-containing bullets. Recycling bismuth from these uses is impractical.[67]

Applications

Black and white engraving of two men extracting and working bismuth, hammering and pouring on a hillside.
18th-century engraving of bismuth processing. During this era, bismuth was used to treat some digestive complaints.

Bismuth has few commercial applications, and those applications that use it generally require small quantities relative to other raw materials. In the United States, for example, 733 tonnes of bismuth were consumed in 2016, of which 70% went into chemicals (including pharmaceuticals, pigments, and cosmetics) and 11% into bismuth alloys.[67]

In the early 1990s, researchers began to evaluate bismuth as a nontoxic replacement for lead in various applications.[67]

Medicines

Bismuth is an ingredient in some pharmaceuticals,[8] although the use of some of these substances is declining.[55]

Cosmetics and pigments

iridescent appearance similar to nacre of pearl. It was used as a cosmetic in ancient Egypt and in many places since. Bismuth white (also "Spanish white") can refer to either bismuth oxychloride or bismuth oxynitrate (BiONO3), when used as a white pigment.[85] Bismuth vanadate is used as a light-stable non-reactive paint pigment (particularly for artists' paints), often as a replacement for the more toxic cadmium sulfide yellow and orange-yellow pigments. The most common variety in artists' paints is a lemon yellow, visually indistinguishable from its cadmium-containing alternative.[86]

Metal and alloys

Bismuth is used in alloys with other metals such as tin and lead. Wood's metal, an alloy of bismuth, lead, tin, and cadmium is used in automatic sprinkler systems for fires. It forms the largest part (50%) of Rose's metal, a fusible alloy, which also contains 25–28% lead and 22–25% tin. It was also used to make bismuth bronze which was used in the Bronze Age, having been found in Inca knives at Machu Picchu.[87]

Lead replacement

The density difference between lead (11.32 g/cm3) and bismuth (9.78 g/cm3) is small enough that for many

less-lethal riot gun ammunition. The Netherlands, Denmark, England, Wales, the United States, and many other countries now prohibit the use of lead shot for the hunting of wetland birds, as many birds are prone to lead poisoning owing to mistaken ingestion of lead (instead of small stones and grit) to aid digestion, or even prohibit the use of lead for all hunting, such as in the Netherlands. Bismuth-tin alloy shot is one alternative that provides similar ballistic performance to lead.[67]

Bismuth, as a dense element of high atomic weight, is used in bismuth-impregnated latex shields to shield from X-ray in medical examinations, such as

CTs, mostly as it is considered non-toxic.[88]

The European Union's Restriction of Hazardous Substances Directive (RoHS) for reduction of lead has broadened bismuth's use in electronics as a component of low-melting point solders, as a replacement for traditional tin-lead solders.[67] Its low toxicity will be especially important for solders to be used in food processing equipment and copper water pipes, although it can also be used in other applications including those in the automobile industry, in the European Union, for example.[89]

Bismuth has been evaluated as a replacement for lead in free-machining brasses for plumbing applications,[90] although it does not equal the performance of leaded steels.[89]

Other metal uses and specialty alloys

Many bismuth alloys have low melting points and are found in specialty applications such as solders. Many automatic sprinklers, electric fuses, and safety devices in fire detection and suppression systems contain the eutectic In19.1-Cd5.3-Pb22.6-Sn8.3-Bi44.7 alloy that melts at 47 °C (117 °F)[18] This is a convenient temperature since it is unlikely to be exceeded in normal living conditions. Low-melting alloys, such as Bi-Cd-Pb-Sn alloy which melts at 70 °C, are also used in automotive and aviation industries. Before deforming a thin-walled metal part, it is filled with a melt or covered with a thin layer of the alloy to reduce the chance of breaking. Then the alloy is removed by submerging the part in boiling water.[91]

Bismuth is used to make

free-machining steels and free-machining aluminium alloys for precision machining properties. It has similar effect to lead and improves the chip breaking during machining. The shrinking on solidification in lead and the expansion of bismuth compensate each other and therefore lead and bismuth are often used in similar quantities.[92][93] Similarly, alloys containing comparable parts of bismuth and lead exhibit a very small change (on the order 0.01%) upon melting, solidification or aging. Such alloys are used in high-precision casting, e.g. in dentistry, to create models and molds.[91] Bismuth is also used as an alloying agent in production of malleable irons[67] and as a thermocouple material.[18]

Bismuth is also used in aluminium-silicon cast alloys to refine silicon morphology. However, it indicated a poisoning effect on modification of

magnetostrictive material, which is used in ultrasonic generators and receivers working in the 10–100 kHz range and in magnetic and holographic memory devices.[96]

Other uses as compounds

Bismuth vanadate, a yellow pigment
  • Bismuth is included in
    BSCCO (bismuth strontium calcium copper oxide) which is a group of similar superconducting compounds discovered in 1988 that exhibit the highest superconducting transition temperatures.[97]
  • CPU coolers, and as detectors in infrared spectrophotometers.[55]
  • Bismuth oxide, in its delta form, is a solid electrolyte for oxygen. This form normally breaks down below a high-temperature threshold, but can be electrodeposited well below this temperature in a highly alkaline solution.[99]
  • Bismuth germanate is a scintillator, widely used in X-ray and gamma ray detectors.[100]
  • lead chromate, it does not blacken due to hydrogen sulfide in the air (a process accelerated by UV exposure) and possesses a particularly brighter color than them, especially the lemon, which is the most translucent, dull, and fastest to blacken due to the higher percentage of lead sulfate required to produce that shade. It is also used, on a limited basis due to its cost, as a vehicle paint pigment.[101][102]
  • A
    acrylic fibers.[18]
  • As an electrocatalyst in the conversion of CO2 to CO.[103]
  • Ingredient in lubricating greases.[104]
  • In crackling microstars (dragon's eggs) in pyrotechnics, as the oxide, subcarbonate or subnitrate.[105][106]
  • As catalyst for the fluorination of arylboronic pinacol esters through a Bi(III)/Bi(V) catalytic cycle, mimicking transition metals in electrophilic fluorination.[107]

Toxicology and ecotoxicology

See also bismuthia, a rare dermatological condition that results from the prolonged use of bismuth.

Scientific literature indicates that some of the compounds of bismuth are less toxic to humans via ingestion than other heavy metals (lead, arsenic, antimony, etc.)[8] presumably due to the comparatively low solubility of bismuth salts.[108] Its biological half-life for whole-body retention is reported to be 5 days but it can remain in the kidney for years in people treated with bismuth compounds.[109]

Bismuth poisoning can occur and has according to some reports been common in relatively recent times.

gingiva, known as a bismuth line.[111][112][113] Poisoning may be treated with dimercaprol; however, evidence for benefit is unclear.[114][115]

Bismuth's environmental impacts are not well known; it may be less likely to bioaccumulate than some other heavy metals, and this is an area of active research.[116][117]

See also

Notes

  1. ^ The thermal expansion is anisotropic: the coefficients for each crystal axis (at 20 °C) are αah = 11.26×10−6/K, αch = 16.74×10−6/K, and αaverage = αvolume/3 = 13.09×10−6/K.

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Cited sources

Public Domain This article incorporates text from this source, which is in the public domain: Brown, R. D., Jr. "Annual Average Bismuth Price", USGS (1998)

External links

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